WO2014123056A1

WO2014123056A1 - Liquid crystal display element and manufacturing method for same

Info

Publication number: WO2014123056A1
Application number: PCT/JP2014/052073
Authority: WO
Inventors: 和樹栗沢; 林　正直; 小川　真治
Original assignee: Dic株式会社
Priority date: 2013-02-06
Filing date: 2014-01-30
Publication date: 2014-08-14
Also published as: EP2955570A4; JPWO2014123056A1; EP2955570A1; EP2955570B1; TWI606113B; JP5741777B2; CN107850809B; KR20150074194A; CN107850809A; US10344214B2; US20160108316A1; TW201804221A; KR101563575B1; TW201435066A; US20170321122A1; US9719017B2; TW201837556A; TWI721283B

Abstract

Provided is a liquid crystal display element and a manufacturing method for the same by which the occurrence of burn-in and of drip marks during manufacturing is mitigated without worsening various characteristics such as dielectric anisotropy, viscosity, nematic phase upper-limit temperature, and rotational viscosity (γ₁). The liquid crystal display element is characterized in that a liquid crystal layer containing a liquid crystal composition is sandwiched between a substrate having a common electrode and a color filter, and a substrate having a plurality of pixels, each of the pixels having a pixel electrode. The liquid crystal display element is further characterized in that the substrates do not have alignment films but have alignment control layers made of two or more polymerizable compounds, the pixels have two or more regions with different pretilt directions, and the liquid crystal composition contains compounds expressed by General Formula (I) and General Formula (II).

Description

Liquid crystal display element and manufacturing method thereof

The present invention relates to a liquid crystal display element useful as a constituent member for a liquid crystal TV or the like and a method for manufacturing the same.

Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, etc., including clocks and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type (vertical alignment; VA) using TFT (thin film transistor), and IPS. (In-plane switching) type. The liquid crystal composition used in these liquid crystal display elements is stable against external factors such as moisture, air, heat, and light, and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature. It is required to be viscous and have a low driving voltage. Furthermore, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to optimize dielectric anisotropy (Δε), refractive index anisotropy (Δn), etc. for each liquid crystal display element. It is composed of

In the VA type display, a liquid crystal composition having a negative Δε is used, which is widely used for liquid crystal TVs and the like. On the other hand, in all driving methods, low voltage driving, high-speed response, and a wide operating temperature range are required. That is, the absolute value of Δε is large, the viscosity (η) is small, and a high nematic phase-isotropic liquid phase transition temperature (T _NI ) is required. Further, from the setting of Δn × d, which is the product of Δn and the cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range according to the cell gap. In addition, when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a low rotational viscosity (γ ₁ ) is required.

On the other hand, in order to improve the viewing angle characteristics of a VA display, an MVA (multi-domain vertical alignment) type that divides the alignment direction of liquid crystal molecules in a pixel into a plurality of parts by providing a protrusion structure on the substrate. Liquid crystal display elements have been widely used. Although the MVA type liquid crystal display element is excellent in view angle characteristics, the response speed of liquid crystal molecules is different between the vicinity of the protrusion structure on the substrate and the part away from the protrusion structure, and the liquid crystal having a slow response speed away from the protrusion structure. Due to the influence of the molecules, there is a problem that the overall response speed is insufficient, and there is a problem of a decrease in transmittance due to the protruding structure. In order to solve this problem, PSA is a method for providing a uniform pretilt angle in a divided pixel without providing a non-transparent protrusion structure in a cell, unlike a normal MVA liquid crystal display element. Liquid crystal display elements (including polymer sustained alignment: polymer sustaining alignment and PS liquid crystal display elements (polymer stabilized)) have been developed. A PSA liquid crystal display element is obtained by adding a small amount of a polymerizable compound to a liquid crystal composition, introducing the liquid crystal composition into a liquid crystal cell, and then applying active energy rays while applying a voltage between the electrodes. It is produced by polymerizing the polymerizable compound. Therefore, an appropriate pretilt angle can be given in the divided pixels, and as a result, high contrast can be achieved by improving the transmittance and high speed response by giving a uniform pretilt angle (see, for example, Patent Document 1). However, in a PSA liquid crystal display element, the addition of a polymerizable compound in the liquid crystal composition causes a problem such as display failure such as image sticking in an active matrix liquid crystal display element that requires a high voltage holding ratio. There was also.

On the other hand, with the increase in the screen size of the liquid crystal display element, the manufacturing method of the liquid crystal display element has also undergone great changes. That is, in the conventional vacuum injection method, when a large panel is manufactured, the manufacturing process takes a lot of time. Therefore, in the manufacture of a large panel, a manufacturing method using an ODF (one-drop-fill) method is mainly used. (For example, see Patent Document 2).
Since this method can shorten the injection time compared with the vacuum injection method, it has become the mainstream method for manufacturing liquid crystal display elements. However, a phenomenon in which a drop mark in which a liquid crystal composition is dropped remains in the liquid crystal display element in a dropped shape after the liquid crystal display element is produced has become a new problem. In addition, a dripping mark is defined as a phenomenon in which a mark in which a liquid crystal composition is dripped appears white when displaying black. In general, the occurrence of dripping marks often depends on the selection of the liquid crystal material, and the cause is not clear.

As a method for suppressing the drop mark, the polymerizable compound mixed in the liquid crystal composition is polymerized to form a polymer layer in the liquid crystal composition layer, thereby suppressing the drop mark generated in relation to the alignment film. A method is disclosed (for example, see Patent Document 3). However, in this method, like the PSA method, there is a problem of display burn-in caused by the polymerizable compound added to the liquid crystal composition, and the effect of suppressing the drop marks is insufficient. There has been a demand for the development of a liquid crystal display element that does not easily cause image sticking or dripping marks while maintaining basic characteristics as a display element.

JP 2002-357830 A JP-A-6-235925 JP 2006-58755 A

The present invention has been made in view of the above circumstances, and does not deteriorate various characteristics such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ) and the like, and is dropped during production and manufacturing. It is an object of the present invention to provide a liquid crystal display element in which generation of a mark is suppressed and a manufacturing method thereof.

In order to solve the above problems, the present inventors have studied various liquid crystal compositions and combinations of methods for imparting a pretilt angle in a liquid crystal display device. As a result, two or more kinds of polymerizable compounds were added to the liquid crystal composition. A substrate constituting the liquid crystal cell in a method of polymerizing the polymerizable compound in the liquid crystal composition by irradiation with active energy rays while applying a voltage between the electrodes after introducing the liquid crystal composition into the liquid crystal cell It has been found that the above-mentioned problems can be solved by combining a specific compound as liquid crystal molecules without providing an alignment film thereon, and the present invention has been completed.

That is, the present invention provides a liquid crystal composition between a first substrate having a common electrode and a color filter layer and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels. A liquid crystal display element in which a liquid crystal layer to be contained is sandwiched between the first substrate and the second substrate and the liquid crystal layer, and does not have an alignment film, and is formed from two or more polymerizable compounds A liquid crystal composition having two or more regions having different pretilt directions in the pixel, wherein the liquid crystal composition has the following general formula (I):

(Wherein R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms) 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.), And the following general formula (II)

(Wherein R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and Q ² represents 1 , 4-phenylene group or trans-1,4-cyclohexylene group, l ² represents 0, 1 or 2, but when l ² is 2, two Q ² are the same or different at best, ^{G 1} is a single _{_{_{bond, -CH 2 CH 2 -, -}}} CH 2 O -, - OCH 2 -, - contains a representative) and a compound represented by - _CF 2 O-or -OCF _2. Provided is a liquid crystal display element characterized by the above.

The present invention also provides a liquid crystal composition between a first substrate having a common electrode and a color filter layer, and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels. A method of manufacturing a liquid crystal display element having a liquid crystal layer contained therein and having two or more regions having different pretilt directions in the pixel, wherein the alignment is performed between the first substrate and the second substrate. Without the film, the following general formula (I)

(Wherein R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms) 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.), A compound represented by the following general formula (II)

(Wherein R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and Q ² represents 1 , 4-phenylene group or trans-1,4-cyclohexylene group, l ² represents 0, 1 or 2, but when l ² is 2, two Q ² are the same or different at best, ^{G 1} is a single _{_{_{bond, -CH 2 CH 2 -, -}}} CH 2 O -, - OCH 2 -, - CF 2 O- or -OCF ₂ -. compounds represented by the representative) a, and 2 Sandwiching a liquid crystal-containing composition for polymerization containing at least one polymerizable compound, By irradiating an active energy ray between the elementary electrode and the common electrode while applying a voltage for applying a pretilt angle to the liquid crystal molecules in the liquid crystal-containing polymerization composition, A polymerizable compound is polymerized, and an alignment control layer is formed between the first substrate and the second substrate and the liquid crystal layer using the liquid crystal-containing polymerization composition as the liquid crystal composition. A method for producing a liquid crystal display element is provided.

According to the present invention, liquid crystal in which image sticking and generation of dripping marks during production are suppressed without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ), etc. A display element and a manufacturing method thereof are provided.

It is a schematic perspective view which shows one Embodiment of the liquid crystal display element of this invention. It is a schematic plan view which shows an example of the slit electrode (comb-shaped electrode) used for the liquid crystal display element of this invention. It is a figure which shows the definition of the pretilt angle in the liquid crystal display element of this invention.

Hereinafter, embodiments of the liquid crystal display element and the manufacturing method thereof of the present invention will be described.
Note that this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

<Liquid crystal display element>
The liquid crystal display element of the present invention is a liquid crystal display element in which a liquid crystal layer containing a liquid crystal composition is sandwiched between a pair of substrates, and a voltage is applied to the liquid crystal layer to displace the liquid crystal molecules in the liquid crystal layer. This is based on the principle of acting as an optical switch by transferring, and a well-known and conventional technique can be used in this respect.
In a normal vertical alignment liquid crystal display element in which two substrates have electrodes for causing the Fredericks transition of liquid crystal molecules, a method of applying a charge vertically between the substrates is generally employed. In this case, one electrode is a common electrode and the other electrode is a pixel electrode. The most typical embodiment of this scheme will be shown below.

FIG. 1 is a schematic perspective view showing an embodiment of the liquid crystal display element of the present invention.
The liquid crystal display element 10 of the present embodiment includes a first substrate 11, a second substrate 12, and a liquid crystal layer that is sandwiched between the first substrate 11 and the second substrate 12 and contains a liquid crystal composition. 13, a common electrode 14 provided on the surface of the first substrate 11 facing the liquid crystal layer 13, a pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal layer 13, A color filter 18 provided between one substrate 11 and the common electrode 14 is schematically configured.

For example, a glass substrate or a plastic substrate is used as the first substrate 11 and the second substrate 12.
As the plastic substrate, a substrate made of a resin such as acrylic resin, methacrylic resin, polyethylene terephthalate, polycarbonate, or cyclic olefin resin is used.

The common electrode 14 and the pixel electrode 15 are usually made of a transparent material such as indium-added tin oxide (ITO).
The pixel electrodes 15 are arranged in a matrix on the second substrate 12. The pixel electrode 15 is controlled by a drain electrode of an active element typified by a TFT switching element (not shown). The TFT switching element has a gate line as an address signal line and a source line as a data line in a matrix. is doing.

The pixel electrode 15 has two or more regions having different pretilt directions of liquid crystal molecules in the pixel. In this way, by defining the pretilt direction of the liquid crystal molecules and dividing the direction in which the liquid crystal molecules fall within the pixel into several regions, the viewing angle characteristics are improved.
When pixel division is performed, for example, a pixel electrode having a slit (a portion where no electrode is formed) having a pattern such as a stripe shape or a V shape may be provided in each pixel.

FIG. 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of a pixel is divided into four regions. The slit electrode has comb-like slits in four directions from the center of the pixel, so that the liquid crystal molecules in each pixel that are substantially perpendicularly aligned with respect to the substrate when no voltage is applied are applied with voltage application. The liquid crystal molecules are directed in four different directions, approaching horizontal alignment. As a result, the alignment direction of the liquid crystal molecules in the pixel can be divided into a plurality of parts, so that the viewing angle characteristic is extremely wide.
As the liquid crystal display element 10, it is preferable that the pixel electrode 15 has a slit (is a slit electrode).

As a method of dividing the pixel, in addition to the method of providing the slit electrode, a method of providing a structure such as a linear protrusion in the pixel, a method of providing an electrode other than the pixel electrode and the common electrode, and the like are applied (not shown). And a method of providing the structure is preferable. The said structure should just have at least one of the 1st board | substrate 11 and the 2nd board | substrate 12, and both may have.
However, a configuration using a slit electrode is preferable from the viewpoint of transmittance and ease of manufacture. Since the slit electrode does not have a driving force for the liquid crystal molecules when no voltage is applied, the slit electrode cannot give a pretilt angle to the liquid crystal molecules. However, in the present invention, a pretilt angle can be imparted by providing an alignment control layer to be described later, and a wide viewing angle by pixel division can be achieved by combining with a slit electrode obtained by pixel division.

In the present invention, having a pretilt angle means that a direction perpendicular to a substrate surface (a surface adjacent to the liquid crystal layer 13 in the first substrate 11 and the second substrate 12) in a state where no voltage is applied, and liquid crystal molecules This means that the direction of the director is slightly different.

Since the liquid crystal display element of the present invention is a vertical alignment (VA) type liquid crystal display element, the director of the liquid crystal molecules is aligned substantially perpendicular to the substrate surface when no voltage is applied. Usually, in order to align liquid crystal molecules vertically, vertical alignment films such as polyimide, polyamide, polysiloxane, etc. are arranged between the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer, respectively. However, the liquid crystal display element of the present invention does not have such an alignment film.

In the liquid crystal display element of the present invention, as in the above-described PSA type liquid crystal display element, an active energy ray such as an ultraviolet ray is irradiated while a voltage is applied between the electrodes and the liquid crystal molecules are slightly tilted. An appropriate pretilt angle is imparted by polymerizing the polymerizable compound in the liquid crystal composition. However, in the liquid crystal display element of the present invention, two or more kinds of polymerizable compounds are used, and an alignment control layer is formed from these polymerizable compounds.

In the present invention, “the liquid crystal molecules are substantially vertically aligned” means a state in which the director of the vertically aligned liquid crystal molecules is slightly tilted from the vertical direction to give a pretilt angle. When the liquid crystal molecules are perfectly vertically aligned, the angle formed by the direction completely parallel to the substrate surface and the direction of the director of the liquid crystal molecules is 90 °, and the liquid crystal molecules are completely homogeneously aligned ( When the liquid crystal molecules are aligned substantially vertically, the angle is preferably 89 to 85 °, more preferably 89 to 87 °. It is.

Two or more kinds of the polymerizable compounds may have any structure different from each other, but preferably include a first polymerizable compound and a second polymerizable compound described below.
Each of the first polymerizable compound and the second polymerizable compound may be used alone or in combination of two or more.

Examples of the first polymerizable compound include those having one polymerizable group, or an alkylene group (one or two in the alkylene group) between two polymerizable groups and these polymerizable groups. The above methylene groups (provided that the number of methylene groups is less than the number of carbon atoms of the alkylene group) are independently oxygen atoms, —CO—, —COO— or Those having — which may be substituted with —OCO— are preferred.
The first polymerizable compound is preferably a (meth) acrylate, and if it has one polymerizable group, it is a monofunctional (meth) acrylate having one (meth) acryloyl group. It is preferable.

In this specification, “(meth) acrylate” means both acrylate and methacrylate, and similarly, “(meth) acryloyl group” means acryloyl group (H ₂ C═CH—CO Both-) and methacryloyl groups (H ₂ C═C (CH ₃ ) —CO—) are meant.
Unless otherwise specified, “—COO—” means “—C (═O) —O—” and “—OCO—” means “—O—C (═O) —”. And

Among them, the first polymerizable compound is represented by the following general formula (X1a)

(In the formula, A ¹ represents a hydrogen atom or a methyl group,
A ² represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. May be)
A ³ and A ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 18 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
A ⁴ and A ⁷ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 9 carbon atoms).
k represents 1 to 40,
B ¹ , B ² and B ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are In addition, as the oxygen atoms are not directly bonded to each other, each may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more of the alkyl groups may be substituted. Each hydrogen atom may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms), or the following general formula (Ib)

(In the formula, A ⁹ represents a hydrogen atom or a methyl group,
A ⁸ represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. A group represented by formula (1). However, among the total of 2 k + 1 B ¹ , B ² and B ³ , the number of the group represented by the general formula (Ib) is 0 or 1. ) A compound represented by
The following general formula (X1b)

(Wherein R ⁷ represents a hydrogen atom or a methyl group,
6-membered rings T ¹ , T ² and T ³ are each independently

(Where m represents an integer of 1 to 4),
n ⁴ represents 0 or 1,
Y ¹ and Y ² are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—. , —CF═CF—, — (CH ₂ ) ₄ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH ₂ ═CHCH ₂ CH ₂ — or —CH ₂ CH ₂ CH = CH-
Y ³ represents a single bond, —COO— or —OCO—,
R ⁸ represents a hydrocarbon group having 1 to 18 carbon atoms. ) A compound represented by
And the following general formula (X1c)

(Wherein R ⁷⁰ represents a hydrogen atom or a methyl group, and R ⁷¹ represents a hydrocarbon group having a condensed ring), and is preferably at least one selected from the group consisting of compounds represented by:

In the present specification, unless otherwise specified, the “alkylene group” is a divalent group obtained by removing one hydrogen atom from each terminal carbon atom of an aliphatic linear or branched hydrocarbon. If there is a substitution from a hydrogen atom to a halogen atom or an alkyl group or a substitution from a methylene group to an oxygen atom, -CO-, -COO- or -OCO-, to that effect Shall be specifically refused. The “alkylene chain length” means, for example, _n in the general formula “— (CH ₂ ) _n — (where n represents an integer of 1 or more)” in the case of a linear alkylene group. It shall be.

In general formula (X1a), the alkyl group having 1 to 18 carbon atoms in A ³ and A ⁶ may be linear, branched or cyclic, but may be linear or branched. Preferably, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl Group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethyl Rupentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Is mentioned.

In the general formula (X1a), examples of the halogen atom in A ³ and A ⁶ include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.

The alkyl group having 1 to 17 carbon atoms in which the hydrogen atom of the alkyl group in A ³ and A ⁶ is substituted is the same as the alkyl group in A ³ and A ⁶ except that the number of carbon atoms is different. Is mentioned.
Further, examples of the halogen atom of the hydrogen atoms of the alkyl group in A ³ and A ⁶ are substituted, include those similar to the aforementioned halogen atom in A ³ and A ^6.

In general formula (X1a), the alkylene group having 1 to 15 carbon atoms in A ² is a divalent group obtained by removing one hydrogen atom from the alkyl group having 1 to 15 carbon atoms in A ³ and A ⁶ . The group of is mentioned.

In general formula (X1a), examples of the alkyl group having 1 to 10 carbon atoms in A ⁴ and A ⁷ include the same groups as the alkyl groups in A ³ and A ⁶ except that the number of carbon atoms is different.
In addition, the alkyl group having 1 to 9 carbon atoms in which the hydrogen atom of the alkyl group in A ⁴ and A ⁷ is substituted is different from the alkyl group in A ³ and A ⁶ except that the number of carbon atoms is different. The same can be mentioned.
Further, examples of the halogen atom of the hydrogen atoms of the alkyl group in A ⁴ and A ⁷ are substituted, include those similar to the aforementioned halogen atom in A ³ and A ^6.

In the general formula (X1a), a linear or branched alkyl group having 1 to 10 carbon atoms in B ¹ , B ² and B ³ is a straight chain having 1 to 10 carbon atoms in A ³ and A ⁶ . The same thing as a chain-like or branched alkyl group is mentioned.
Further, the trialkoxysilyl group having 3 to 6 carbon atoms in which the hydrogen atom of the alkyl group in B ¹ , B ² and B ³ is substituted includes any one of a methoxy group and an ethoxy group as the alkoxy group. 3 may be bonded to the same silicon atom, and the three alkoxy groups bonded to the same silicon atom may all be the same or only two may be the same. Specifically, a trimethoxysilyl group, a triethoxysilyl group, an ethoxydimethoxysilyl group, a diethoxymethoxysilyl group, and the like can be given.
In addition, examples of the halogen atom in which the hydrogen atom of the alkyl group in B ¹ , B ^2, and B ³ is substituted include the same halogen atoms as those in A ³ and A ⁶ .

In the general formula (X1a), B ¹ , B ² and B ³ are present in total 2k + 1, of which the number of the groups represented by the general formula (Ib) is 0 or 1. The group represented by the general formula (Ib) may be any of B ¹ , B ² and B ³ , but is preferably B ¹ .

Among the compounds represented by the general formula (X1a), B ¹ , B ² or B ³ is a group represented by the above general formula (Ib), and preferred examples thereof include the following general formula (X1a -1)

(In the formula, A ¹¹ and A ¹⁹ each independently represent a hydrogen atom or a methyl group;
A ¹² and A ¹⁸ are each independently a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are such that oxygen atoms are not directly bonded to each other). Each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkylene group are each independently a fluorine atom, Which may be substituted with a methyl group or an ethyl group)
A ¹³ and A ¹⁶ each independently represents a linear alkyl group having 2 to 20 carbon atoms (one or two or more methylene groups in the linear alkyl group have an oxygen atom Each of which may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO— as a non-direct bond.
A ¹⁴ and A ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other). Each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom or Which may be substituted with an alkyl group of 1 to 9 carbon atoms)
A ¹⁵ represents an alkylene group having 9 to 16 carbon atoms (in at least 1 to 5 methylene groups in the alkylene group, one hydrogen atom in the methylene group independently represents 1 to 10 carbon atoms). In the alkylene group, one or two or more methylene groups may be independently selected as those in which oxygen atoms are not directly bonded to each other. And may be substituted with an oxygen atom, —CO—, —COO— or —OCO—. ) A compound represented by
The following general formula (X1a-2)

(Wherein A ²¹ and A ²² each independently represents a hydrogen atom or a methyl group, and a represents an integer of 6 to 22),
The following general formula (X1a-3)

(Wherein A ³¹ and A ³² each independently represent a hydrogen atom or a methyl group, b, c and d each independently represents an integer of 1 to 10, and e represents an integer of 0 to 6). ) A compound represented by
And the following general formula (X1a-4)

(Wherein A ⁴¹ and A ⁴² each independently represents a hydrogen atom or a methyl group, and m, n, p and q each independently represents an integer of 1 to 10). 1 or more types chosen from a group are mentioned.

In the general formula (X1a-1), the linear alkyl group having 2 to 20 carbon atoms in A ¹³ and A ¹⁶ is the same as the linear alkyl group in A ³ and A ⁶ ; Nonadecyl group, icosyl group, etc. are mentioned.
In general formula (X1a-1), examples of the alkyl group having 1 to 10 carbon atoms in A ¹⁴ and A ¹⁷ include the same alkyl groups as those in A ³ and A ⁶ except that the number of carbon atoms is different. It is done.
In general formula (X1a-1), examples of the alkylene group having 1 to 15 carbon atoms for A ¹² and A ¹⁸ include the same alkylene groups as those described above for A ² .
In general formula (X1a-1), the alkylene group having 9 to 16 carbon atoms in A ¹⁵ is obtained by removing one hydrogen atom from the alkyl group having 9 to 16 carbon atoms in A ³ and A ⁶ A divalent group is mentioned.
An alkyl group having 1 to 9 carbon atoms in which a hydrogen atom of the alkyl group in A ¹⁴ and A ¹⁷ is substituted; and a straight chain having 1 to 10 carbon atoms in which a hydrogen atom of the alkylene group in A ¹⁵ is substituted. Examples of the chain or branched alkyl group include the same alkyl groups as those described above for A ³ and A ⁶ except that the number of carbon atoms is different.
Further, examples of the halogen atom of the hydrogen atoms of the alkyl group in A ¹⁴ and A ¹⁷ are substituted, include those similar to the aforementioned halogen atom in A ³ and A ^6.

The compound represented by the general formula (X1a-1) is such that A ¹¹ and A ¹⁹ are both hydrogen atoms in that the polymerization rate is faster than that in which both A ¹¹ and A ¹⁹ are methyl groups. Those are preferred.

In the compound represented by the general formula (X1a-1), it is preferable that A ¹² and A ¹⁸ are each independently a single bond or an alkylene group having 1 to 3 carbon atoms. The distance between two polymerizable groups can be adjusted by changing the length of carbon number independently for A ¹² and A ¹⁸ and A ¹⁵ . The feature of the compound represented by the general formula (X1a-1) is that the distance between the polymerizable groups (distance between the crosslinking points) is long, but if this distance is too long, the polymerization rate becomes extremely slow. There is an upper limit on the distance between the polymerizable groups because it adversely affects the phase separation. On the other hand, the distance between the two side chains of A ¹³ and A ¹⁶ also affects the mobility of the main chain. That is, if the distance between A ¹³ and A ¹⁶ is short, side chains A ¹³ and A ¹⁶ will interfere with each other, resulting in a decrease in mobility. Accordingly, in the compound represented by the general formula (X1a-1), the distance between the polymerizable groups is determined by the sum of A ¹² , A ¹⁸ , and A ¹⁵ , and among these, A ¹² is longer than A ¹² and A ¹⁸ are made longer. It is preferable to make ¹⁵ longer.

On the other hand, in the side chains A ¹³ , A ¹⁴ , A ¹⁶ , and A ¹⁷ , the lengths of these side chains are preferably as follows.

In general formula (X1a-1), A ¹³ and A ¹⁴ are bonded to the same carbon atom in the main chain, but when their lengths are different, the longer side chain is referred to as A ¹³ ( If the length and the length of ^{a 14} of a ¹³ are equal, one to one and ^{a 13).} Similarly, when the length of the length and A ¹⁷ of A ¹⁶ are different, if the length and the length of A ¹⁷ in the longer side chain of is referred to as A ¹⁶ (A ¹⁶ are equal, either the one and a ^16).

In the present invention, such A ¹³ and A ¹⁶ are each independently a linear alkyl group having 2 to 20 carbon atoms (one or two or more present in the linear alkyl group). These methylene groups are each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, assuming that oxygen atoms are not directly bonded to each other. , Each independently a linear alkyl group having 2 to 18 carbon atoms (one or two or more methylene groups present in the linear alkyl group are those in which oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and more preferably each independently a straight chain of 3 to 15 carbon atoms. An alkyl group (the linear alkyl One or more methylene groups present in the group may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, assuming that the oxygen atoms are not directly bonded to each other. Good.)

Since the side chain has higher mobility than the main chain, its presence contributes to improvement of the mobility of the polymer chain at low temperature, but as mentioned above, spatial interference occurs between the two side chains. On the contrary, motility decreases. In order to prevent such spatial interference between side chains, it is effective to increase the distance between the side chains and to shorten the side chain length within a necessary range.

In the present invention, A ¹⁴ and A ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group are oxygen atoms). Are each independently substituted with an oxygen atom, —CO—, —COO— or —OCO— so that they are not directly bonded to each other, and one or more hydrogen atoms present in the alkyl group Are each independently substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms.), But preferably each independently an hydrogen atom or an alkyl having 1 to 7 carbon atoms. A group (one or two or more methylene groups present in the alkyl group are each independently an oxygen atom, —CO—, —COO— or —OCO—, as oxygen atoms are not directly bonded to each other); More preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (one or two or more methylene groups present in the alkyl group are Oxygen atoms may be independently substituted with oxygen atoms, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other, and more preferably each independently a hydrogen atom. Or an alkyl group having 1 to 3 carbon atoms (one or two or more methylene groups present in the alkyl group are each independently an oxygen atom, —CO—, It may be substituted with —COO— or —OCO—.

For even A ¹⁴ and A ^17, the it is too long length it is not preferred to induce spatial interference between side chains. On the other hand, when A ¹⁴ and A ¹⁷ is an alkyl chain of short length, high to motility can become a side chain having, and is considered to have a function of inhibiting the approach of adjacent main chain between The action of preventing the interference between the polymer main chains is considered to increase the mobility of the main chains, and it is possible to suppress the anchoring energy from increasing at low temperatures, and the polymer stabilized liquid crystal This is effective in improving the display characteristics of the display element in a low temperature range.

A ¹⁵ located between the two side chains is preferably longer in terms of changing the distance between the side chains and also in increasing the distance between the crosslinking points to lower the glass transition point. However, when A ¹⁵ is too long, the general formula becomes too large molecular weight of the compound represented by (X1a-1), the compatibility with the liquid crystal composition is lowered, and the polymerization rate decreases There is an upper limit on the length of the length, for example, because the phase separation is adversely affected.

Accordingly, A ¹⁵ represents an alkylene group having 9 to 16 carbon atoms (in at least 1 to 5 methylene groups in the alkylene group, each hydrogen atom in the methylene group independently represents 1 carbon atom). May be substituted with 10 to 10 linear or branched alkyl groups, and one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other. And may be substituted with an atom, —CO—, —COO— or —OCO—.

That is, the alkylene chain length of A ¹⁵ is preferably 9 to 16 carbon atoms. When the hydrogen atom in the alkylene group for A ¹⁵ is substituted with an alkyl group having 1 to 10 carbon atoms, the number of substitution of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and more preferably 2 or 3 More preferably. The number of carbon atoms in the substituted alkyl group is preferably 1 to 5, more preferably 1 to 3.

The compounds represented by the general formula (X1a-1) are “Tetrahedron Letters, Vol. 30, pp 4985”, “Tetrahedron Letters, Vol. , Vol. 34, pp 217-225 "and the like.

For example, in the general formula (X1a-1), a compound in which A ¹⁴ and A ¹⁷ are hydrogen includes a compound having a plurality of epoxy groups and a polymer such as acrylic acid or methacrylic acid having active hydrogen capable of reacting with the epoxy group. It can be obtained by reacting with a functional compound to synthesize a polymerizable compound having a hydroxyl group and then reacting with a saturated fatty acid.
Furthermore, by reacting a compound having a plurality of epoxy groups with a saturated fatty acid, synthesizing a compound having a hydroxyl group, and then reacting a polymerizable compound such as an acrylate chloride having a group capable of reacting with a hydroxyl group. can get.

In the case where the radical polymerizable compound is, for example, A ¹⁴ and A ^{17 in} the general formula (X1a-1) are alkyl groups and A ¹² and A ¹⁸ are methylene groups having 1 carbon atom, an oxetane group And a method of reacting a fatty acid chloride or a fatty acid capable of reacting with an oxetane group with a polymerizable compound having active hydrogen such as acrylic acid, or a compound having one oxetane group It can be obtained by a method of reacting a polyvalent fatty acid chloride or a fatty acid capable of reacting with an oxetane group and further reacting a polymerizable compound having active hydrogen such as acrylic acid.
Further, when A ¹² and A ¹⁸ in the general formula (X1a-1) are an alkylene group having 3 carbon atoms (propylene group, —CH ₂ CH ₂ CH ₂ —), a furan group is used instead of the oxetane group. It can be obtained by using a compound having a plurality of. Further, when A ¹² and A ¹⁸ in the general formula (X1a-1) are an alkylene group having 4 carbon atoms (butylene group, —CH ₂ CH ₂ CH ₂ CH ₂ —), instead of the oxetane group It can be obtained by using a compound having a plurality of pyran groups.
Of the compounds of the general formula (X1a-1) thus obtained, the following general formula (X1a-1-1)

(In the formula, A ¹¹ and A ¹⁹ each independently represent a hydrogen atom or a methyl group;
A ¹² ′ and A ¹⁸ ′ each represent a methylene group;
A ¹³ and A ¹⁶ are each independently a linear alkyl group having 2 to 20 carbon atoms (one or two or more methylene groups present in the linear alkyl group are such that oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-)
A ¹⁴ ′ and A ¹⁷ ′ each independently represents an alkyl group having 1 to 10 carbon atoms,
A ¹⁵ represents an alkylene group having 9 to 16 carbon atoms (in the alkylene group, at least 1 to 5 methylene groups, each hydrogen atom in the methylene group independently represents one having 1 to 10 carbon atoms). It may be substituted with a linear or branched alkyl group, and one or two or more methylene groups in the alkylene group are each independently an oxygen atom,- CO—, —COO— or —OCO— may be substituted. ) Is preferred.

Examples of the alkyl group for A ¹⁴ ′ and A ¹⁷ ′ include the same alkyl groups as those for A ¹⁴ and A ¹⁷ .

In the compound represented by the general formula (X1a-1-1), the total number of —COO— and —OCO— in A ¹⁵ is 2 or less, and —COO— and —OCO in A ¹³ and A ¹⁶ Particularly preferred are those in which each of-is 1 or less, and specific examples include compounds represented by the following formulas (X1a-101) to (X1a-109).

In the general formula (X1b), the hydrocarbon group having 1 to 18 carbon atoms in R ⁸ may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is linear These may be branched or cyclic, and may be any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group. The cyclic hydrocarbon group may be either monocyclic or polycyclic.
Among them, the hydrocarbon group having 1 to 18 carbon atoms in R ⁸ is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, and carbon atoms in A ³ and A ⁶ Examples thereof include the same alkyl groups having 1 to 18 atoms, and a linear or branched saturated aliphatic hydrocarbon group is particularly preferable.

Preferred examples of the compound represented by the general formula (X1b) include those in which the 6-membered rings T ¹ , T ² and T ³ are all hydrocarbon rings.

In the compound represented by the general formula (X1c), the hydrocarbon group of R ⁷¹ may be any one having a condensed ring, may be composed only of a condensed ring, or may be a condensed ring and other hydrocarbon groups. You may have.
The condensed ring may be either an aliphatic ring or an aromatic ring. The aliphatic ring may be either a saturated aliphatic ring or an unsaturated aliphatic ring, and may have both a saturated aliphatic ring and an unsaturated aliphatic ring. The number of rings constituting the condensed ring may be two or more, but preferably 2 to 7.
The hydrocarbon group other than the condensed ring may be linear, branched or cyclic, and may have both a linear (linear and / or branched) structure and a cyclic structure. The chain structure and cyclic structure hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group, and the cyclic structure hydrocarbon group may be an aliphatic ring hydrocarbon group or an aromatic hydrocarbon group. Either is acceptable.
Preferred examples of R ⁷¹ include a monovalent group obtained by removing one hydrogen atom from a steroid, and a monovalent group obtained by removing a hydroxyl group from cholesterol is preferred.

As said 2nd polymeric compound, what has two polymeric groups which do not correspond to a 1st polymeric compound is preferable, for example.
The second polymerizable compound is preferably (meth) acrylate, and is preferably bifunctional (meth) acrylate having two (meth) acryloyl groups.

Among them, the second polymerizable compound is represented by the following general formula (X2a)

(Wherein R ³ and R ⁴ each independently represents a hydrogen atom or a methyl group,
C ⁴ and C ⁵ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyridazine-3,6- Diyl group, 1,3-dioxane-2,5-diyl group, cyclohexene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6 -Diyl group, phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, 2,6-naphthylene group or indane-2,5-diyl group (among these groups, 1,4-phenylene group) 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group and indane-2,5-diyl group each independently have one or more hydrogen atoms. Fluorine atom, Represents atom, a methyl group, may be substituted with a trifluoromethyl group or a trifluoromethoxy group. The)
Z ³ and Z ⁵ are each independently a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are such that oxygen atoms are not directly bonded to each other; Each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkylene group are each independently a fluorine atom, methyl Group or an ethyl group, which may be substituted)
Z ⁴ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CH ₂ CH ₂ O—, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ O—, —OCH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ OCO—, —COOCH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, —OCOCH ₂ CH ₂ —, —CH═CH—, —C≡C— , —CF ₂ O—, —OCF ₂ —, —CH═CHCOO—, —OCOCH═CH—, —COO— or —OCO—,
n ² represents 0, 1 or 2, and when n ² is 2, a plurality of C ⁴ and Z ⁴ may be the same or different. It is preferably at least one selected from the group consisting of compounds represented by

In the general formula (X2a), as the alkylene group having 1 to 15 carbon atoms in Z ³ and Z ^5, one hydrogen atom is removed from the alkyl group having 1 to 15 carbon atoms in A ³ and A ⁶ . And a divalent group.

Preferred examples of the second polymerizable compound include compounds represented by the following formulas (X2a-101) to (X2a-140).

The polymerizable compound used for the formation of the orientation control layer may be two or more types, but it does not deteriorate the various characteristics as a liquid crystal display element and the image sticking characteristics of the liquid crystal display element. 2 to 4 types are preferable, 2 to 3 types are more preferable, and 2 types are particularly preferable.

The ratio of each of the polymerizable compounds used for forming the orientation control layer may be appropriately adjusted depending on how many kinds of the polymerizable compounds are used, but the ratio of the polymerizable compound to the total amount used is 10 to 90%. The content is preferably mass%, more preferably 14 to 86 mass%.
In particular, when only one each of the first polymerizable compound and the second polymerizable compound is used to form the orientation control layer, the use of the first polymerizable compound with respect to the amount of the second polymerizable compound used The amount is preferably 1 to 8 times by mass, and more preferably 1.5 to 6 times by mass.

The liquid crystal composition has the following general formula (I)

(Wherein R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms) 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.)
And the following general formula (II)

(Wherein R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and Q ² represents 1 , 4-phenylene group or trans-1,4-cyclohexylene group, l ² represents 0, 1 or 2, but when l ² is 2, two Q ² are the same or different at best, ^{G 1} is a single _{_{_{bond, -CH 2 CH 2 -, -}}} CH 2 O -, - OCH 2 -, - contains a representative) and a compound represented by - _CF 2 O-or -OCF _2. .

In general formula (I), the alkyl group having 1 to 8 carbon atoms in R ^1α and R ^2α may be linear, branched or cyclic, but may be linear or branched. Preferably, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl Group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethyl Pentyl group, 2,2,3-trimethyl butyl group, n- octyl group, and isooctyl group.
The alkyl group in R ^1α and R ^2α preferably has 1 to 6 carbon atoms.

In general formula (I), ^examples of the alkenyl group having 2 to 8 carbon atoms in R ^1α and R ^2α include ethenyl group (vinyl group), 2-propenyl group (allyl group), etc., and carbon atoms in R ^1α and R ^2α Examples of the alkyl group represented by Formulas 2 to 8 include monovalent groups in which one single bond (C—C) between carbon atoms is substituted with a double bond (C═C).
The alkenyl group in R ^1α and R ^2α preferably has 2 to 6 carbon atoms, and more preferably has the following structure.

(In the formula, the rightmost carbon atom of the alkenyl group is bonded to the ring structure.)

In general formula (I), the alkoxy group having 1 to 8 carbon atoms in R ^1α and R ^2α is a methoxy group, an ethoxy group, or the like, and the alkyl group having 1 to 8 carbon atoms in R ^1α and R ^2α is oxygen. A monovalent group formed by bonding to an atom is exemplified.
The alkoxy group in R ^1α and R ^2α preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

In the formula (I), the alkenyloxy group ^{R l [alpha]} and ^{R 2.alpha} having 2 to 8 carbon atoms in, ethenyloxy group, 2-propenyloxy group, wherein the ^{R l [alpha]} and 2 to 8 carbon atoms in ^{R 2.alpha} Examples thereof include a monovalent group in which an alkenyl group is bonded to an oxygen atom.
The alkenyloxy group in R ^1α and R ^2α preferably has 2 to 6 carbon atoms.

Preferred compounds represented by the general formula (I) include those in which the combination of R ^1α and R ^2α is the alkyl group, the alkyl group and the alkoxy group, the alkyl group and the alkenyl group. Some are listed.
Preferred examples of the compound represented by the general formula (I) include those represented by the following general formulas (I-1) to (I-4).

(In the formula, R ^1α and R ^2α are the same as described above.)

The content of the compound represented by the general formula (I) in the liquid crystal composition is preferably 30 to 65% by mass, and more preferably 35 to 55% by mass.

In the general formula (II), R ^3α is the same as R ^1α and R ^2α .
In general formula (II), ^examples of the alkyl group and alkoxy group having 1 to 8 carbon atoms in R ^4α include the same as the alkyl group and alkoxy group having 1 to 8 carbon atoms in R ^1α and R ^2α . .
In the general formula (II), the alkenyl group having 4 to 8 carbon atoms and the alkenyloxy group having 3 to 8 carbon atoms in R ^4α are the same as those in R ^1α and R ^2α except that the number of carbon atoms is different. The same thing as an alkenyl group and an alkenyloxy group is mentioned.

The alkyl groups in R ^3α and R ^4α preferably each independently have 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms.
The alkoxy groups in R ^3α and R ^4α preferably each independently have 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms.

Preferred compounds represented by the general formula (II) are those in which R ^3α is the alkyl group, R ^4α is the alkoxy group, l ² is 0 or 1, and G ¹ is simple. What is a bond is mentioned.
In addition, preferred examples of the compound represented by the general formula (II) include those represented by the following general formulas (II-1) to (II-3).

(In the formula, R ^3α and R ^4α are the same as described above.)

The content of the compound represented by the general formula (II) in the liquid crystal composition is preferably 30 to 65% by mass, and more preferably 35 to 55% by mass.

In the liquid crystal composition, [content of compound represented by general formula (II)] / [content of compound represented by general formula (I)] (mass ratio) is 8/2 to 2/8. Is preferable, 7/3 to 3/7 is more preferable, and 6/4 to 4/6 is particularly preferable.

In addition to the compounds represented by the general formulas (I) and (II), the liquid crystal composition includes the following general formula (III)

Wherein R ^5α and R ^6α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 alkenyloxy groups (one or two or more methylene groups in the alkyl group, alkenyl group, alkoxy group or alkenyloxy group independently represent oxygen atoms or -CO- may be substituted with one or two or more hydrogen atoms in the alkylene group represents may be substituted by a fluorine atom.), Q ³ is 1,4-phenylene group or Represents a tetrahydropyran-2,5-diyl group, l ³ represents 0 or 1, G ² represents a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —. , ^{^L} 1 ~ ^L ⁶ is, Represents a respectively independently a hydrogen atom or a fluorine atom, at least two L 1 ^~ L ⁶ represents a fluorine atom, if and G ² l ³ represents 0 represents a single bond, L ⁵ and L ⁶ may not contain a fluorine atom.) May be contained.

In the general formula (III), an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms and an alkoxy group having 2 to 8 carbon atoms in R ^5α and R ^6α The alkenyloxy group is the same as in R ^1α and R ^2α .

Preferred examples of the compound represented by the general formula (III) include, for example, the following general formula (III-1)

(Wherein, R ^5α and R ^6α are the same as described above).

Further, the liquid crystal composition includes the following general formula (IV) which does not correspond to the compounds other than the compounds represented by the general formulas (I) and (II).

( ^Wherein R ^7α and R ^8α each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms). It may contain the compound.

In general formula (IV), the alkyl group having 1 to 10 carbon atoms in R ^7α and R ^8α may be linear, branched or cyclic, but may be linear or branched. Preferably, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl Group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethyl Rupenchiru group, 2,2,3-trimethyl butyl group, n- octyl group, an isooctyl group, a nonyl group, decyl group.
The alkyl group in R ^1α and R ^2α preferably has 1 to 6 carbon atoms.

In formula (IV), Examples of the alkenyl group having 2 to 10 carbon atoms in the ^{R 7.alpha} and ^{R 8α,} in the alkyl group having 2 to 10 carbon atoms in the ^{R 7.alpha} and ^{R 8α,} the one between carbon atoms Examples thereof include a monovalent group in which a single bond (C—C) is substituted with a double bond (C═C).
The alkenyl group in R ^7α and R ^8α preferably has 2 to 6 carbon atoms, and examples thereof include the same as those in R ^1α and R ^2α .

In the general formula (IV), the alkoxy group having 1 to 10 carbon atoms in R ^7α and R ^8α is a methoxy group, an ethoxy group, or the like, and the alkyl group having 1 to 10 carbon atoms in R ^7α and R ^8α is oxygen. A monovalent group formed by bonding to an atom is exemplified.

In addition to the compounds represented by the general formulas (I) and (II), the liquid crystal composition includes the following general formula (V) that does not correspond to these compounds.

Wherein R ^9α and R ^10α are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 18 represents an alkenyloxy group, Q ⁴ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and l ⁴ represents 0 or 1. Good.

In general formula (V), the alkyl group having 1 to 18 carbon atoms in R ^9α and R ^10α may be linear, branched or cyclic, but may be linear or branched. Preferably, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl Group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethyl Rupentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Is mentioned.
The alkyl group in R ^9α and R ^10α preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

In formula (V), Examples of the alkenyl group having 2 to 18 carbon atoms in the ^{R 9.alpha} and ^{R 10 [alpha],} in the alkyl group of ^{R 9.alpha} and ^{R 10 [alpha]} 2 to 18 carbon atoms in, the one between carbon atoms Examples thereof include a monovalent group in which a single bond (C—C) is substituted with a double bond (C═C).
The alkenyl group in R ^9α and R ^10α preferably has 2 to 6 carbon atoms, and examples thereof include the same ones as in R ^1α and R ^2α .

In the general formula (V), the alkoxy group having 1 to 18 carbon atoms in R ^9α and R ^10α is a methoxy group, an ethoxy group, or the like, and the alkyl group having 1 to 18 carbon atoms in R ^9α and R ^10α is oxygen. A monovalent group formed by bonding to an atom is exemplified.
The alkoxy group in R ^9α and R ^10α preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

In general formula (V), examples of the alkenyloxy group having 2 to 18 carbon atoms in R ^9α and R ^10α include an ethenyloxy group, a 2-propenyloxy group, etc., and those having 2 to 18 carbon atoms in R ^9α and R ^10α Examples thereof include a monovalent group in which an alkenyl group is bonded to an oxygen atom.

Preferred examples of the compound represented by the general formula (V) include, for example, the following general formula (V-1)

(Wherein, R ^9α and R ^10α are the same as described above).

The content of the components other than the compounds represented by the general formulas (I) and (II) such as the compounds represented by the general formulas (III), (IV), and (V) in the liquid crystal composition is 25. It is preferable that it is mass% or less, and it is more preferable that it is 20 mass% or less.

The liquid crystal display element 10 may further include a passivation film between at least one of the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13 ( (Not shown). As described above, the surface of the first substrate 11 or the second substrate 12 in the vicinity is protected by having the passivation film.

The liquid crystal display element 10 may further include a planarization film between at least one of the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13. (Not shown). As described above, by having the planarizing film, various characteristics as the liquid crystal display element are further improved. If the surface of the passivation film has high flatness, the passivation film may be handled as a flattening film.

As the passivation film and the planarizing film, known ones can be used as appropriate.

The liquid crystal display element of the present invention includes a liquid crystal composition using a specific compound represented by general formulas (I) and (II) as liquid crystal molecules, an alignment control layer formed from two or more polymerizable compounds, and In combination with the liquid crystal display element, unlike the conventional liquid crystal display element, there is no need to have alignment films between the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer. When no voltage is applied, the liquid crystal molecules are aligned substantially perpendicular to the substrate surface. Further, image sticking and generation of dripping marks during production are suppressed without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ) and the like.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element 10 shown in FIG. 1 can be manufactured by the following method, for example.
First, the first substrate 11 and the second substrate 12 are overlapped, and a liquid crystal-containing polymerization composition for forming the liquid crystal layer 13 and the alignment control layer is sandwiched between them by a process described later. The liquid crystal-containing polymerization composition is
It contains the compound represented by the general formula (I), the compound represented by the general formula (II), and two or more kinds of the polymerizable compounds as essential components.

More specifically, spacer protrusions for securing a cell gap, such as plastic beads, are sprayed on the facing surfaces of either the first substrate 11 or the second substrate 12. At the same time, for example, the seal portion is printed (formed) by screen printing using an epoxy adhesive or the like. The surface of the first substrate 11 facing the second substrate 12 is the surface having the common electrode 14 and the color filter 18, and the surface of the second substrate 12 facing the first substrate 11 is The surface having the pixel electrode 15.

Next, the first substrate 11 and the second substrate 12 are made to face each other, and these are bonded together via the spacer protrusion and the seal portion, and then the liquid crystal-containing polymerization composition is injected into the formed space. To do. Then, the liquid crystal-containing polymerization composition is sandwiched between the first substrate 11 and the second substrate 12 by curing the seal portion by heating or the like.

Next, a voltage is applied between the common electrode 14 and the pixel electrode 15 using voltage applying means. The voltage at this time is 5 to 30 V, for example. Thereby, the adjacent surface (surface which opposes the composition for liquid crystal containing polymerization) of the 1st board | substrate 11 and the composition for liquid crystal containing polymerization of the 2nd board | substrate 12 (surface which opposes the composition for liquid crystal containing polymerization) ( An electric field having a predetermined angle is generated with respect to the liquid crystal-containing polymerization composition, and the liquid crystal molecules in the liquid crystal-containing polymerization composition (compound represented by general formula (I), general formula The compound (II) (19) is oriented in a predetermined direction with respect to the normal direction of the first substrate 11 and the second substrate 12, and as shown in FIG. Is granted. The magnitude of the pretilt angle θ can be controlled by appropriately adjusting the magnitude of the voltage.

Next, the two or more polymerizable compounds are polymerized by irradiating an active energy ray such as ultraviolet rays from the outside of the first substrate 11 to the liquid crystal-containing polymerization composition while the voltage is applied. Let The active energy ray may be irradiated from the outside of the second substrate 12 or may be irradiated from both the outside of the first substrate 11 and the outside of the second substrate 12.
By irradiation with active energy rays, two or more kinds of the polymerizable compounds in the liquid crystal-containing polymerization composition react, and the liquid crystal-containing polymerization composition becomes a liquid crystal composition having a desired composition to form the liquid crystal layer 13. At the same time, an alignment control layer is formed between the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13.

The formed alignment control layer imparts a pretilt angle θ to the liquid crystal molecules 19 located in the vicinity of the first substrate 11 and in the vicinity of the second substrate 12 in the liquid crystal layer 13 in a non-driven state.

The irradiation intensity of the active energy ray may or may not be constant, and when changing the irradiation intensity, the irradiation time at each irradiation intensity can be arbitrarily set, but two or more stages When the irradiation process is adopted, the irradiation intensity of the irradiation process after the second stage is preferably weaker than the irradiation intensity of the irradiation process of the first stage, and the total irradiation time of the irradiation process after the second stage is It is preferable that the irradiation time is longer than the first stage irradiation time and the total irradiation energy amount is large. In addition, when the irradiation intensity is changed discontinuously, the average irradiation light intensity in the first half of the entire irradiation process time is preferably stronger than the average irradiation intensity in the second half, and the intensity immediately after the start of irradiation is the strongest. More preferably, the irradiation intensity always decreases to a certain value as the irradiation time elapses. The irradiation intensity of the active energy ray in this case is preferably 2 to 100 mW / cm ² , but it is the highest in all irradiation processes in the first stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. The irradiation intensity is 10 to 100 mW / cm ² , and the minimum irradiation intensity is 2 to 50 mW / cm ² after the second stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. It is more preferable. The total irradiation energy amount is preferably 10 to 300 J, more preferably 50 to 250 J, and further preferably 100 to 250 J.
The applied voltage may be alternating current or direct current.

The irradiated active energy rays preferably have a plurality of spectra, and ultraviolet rays having a plurality of spectra are preferable. By irradiation with active energy rays having a plurality of spectra, two or more kinds of the polymerizable compounds can be polymerized by active energy rays having a spectrum (wavelength) suitable for each type, and in this case, the orientation control layer Is formed more efficiently.

The alignment control layer is composed of a polymer of the polymerizable compound. For example, the first substrate 11 and the liquid crystal layer 13 are not clearly separated and formed between them. In the vicinity of the substrate 11, it is estimated that the first substrate 11 may be formed so as to enter the liquid crystal layer 13 from a surface adjacent to the liquid crystal layer 13 (a surface facing the liquid crystal layer 13). The The same is true in the vicinity of the second substrate 12, and the alignment control layer is not necessarily formed between the second substrate 12 and the liquid crystal layer 13 by clearly dividing the second substrate 12. In the vicinity of, it is estimated that the second substrate 12 may be formed so as to enter the liquid crystal layer 13 from a surface adjacent to the liquid crystal layer 13 (a surface facing the liquid crystal layer 13).
However, it is difficult to accurately indicate the structure of the orientation control layer.

Further, by irradiation with active energy rays, the two or more kinds of polymerizable compounds are preferentially polymerized with each other having similar structures to align liquid crystal molecules in the vicinity region of the substrate, and the direction of the pretilt. It is presumed that the orientation is controlled by defining the value in a predetermined direction.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, “wt%” means mass%.

In the following examples and comparative examples, T _NI , Δn, Δε, η, and γ ₁ are defined as follows.
T _NI : Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 25 ° C. Δε: Dielectric anisotropy at 25 ° C. η: Viscosity at 20 ° C. (mPa · s)
γ ₁ : rotational viscosity at 25 ° C. (mPa · s)

The liquid crystal display elements manufactured in the following Examples and Comparative Examples were evaluated for image sticking and dropping marks by the following methods.

(Evaluation of burn-in)
Evaluation of burn-in of the liquid crystal display element is performed by visually confirming the level of the afterimage of the fixed pattern when the predetermined fixed pattern is displayed in the display area for 1000 hours and then the entire screen is uniformly displayed. The four grades were evaluated.
◎: No afterimage ○: Even afterimage is slightly acceptable but acceptable △: Afterimage is acceptable Unacceptable level ×: Afterimage is quite poor

(Evaluation of dripping marks)
Evaluation of the drop mark of the liquid crystal display device was performed by visually confirming the drop mark that appeared white when the entire surface was displayed in black, and was evaluated in the following four stages.
◎: No afterimage ○: Even afterimage is very slight but acceptable level △: Afterimage is present and unacceptable level ×: Afterimage is present

(Example 1)
A first substrate (a common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (a pixel electrode substrate) having a transparent pixel electrode driven by an active element were produced. . As the pixel electrode, a pixel electrode divided into four regions having different pretilt directions by using a slit was used.
A liquid crystal-containing raw material composition LC-1 containing the following compounds corresponding to the general formulas (I), (II) and (III) in the ratios shown below was prepared.

Next, the first polymerizable compound represented by the general formula (X1a) ((X1a-1-1)) with respect to the liquid crystal-containing raw material composition LC-1 (98.0% by mass),

A compound represented by the formula (1.5% by mass) and a second polymerizable compound represented by the general formula (X2a):

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -1 was prepared.

Next, after bonding the first substrate and the second substrate through the seal portion, the liquid crystal-containing polymerization composition CLC-1 is injected without using an alignment film, the seal portion is cured, and the liquid crystal The containing polymerization composition CLC-1 was sandwiched. At this time, the thickness of the layer made of the liquid crystal-containing polymerization composition was set to 3.2 μm using a spacer having a thickness of 3.2 μm.
Next, while the voltage was applied, the liquid crystal-containing polymerization composition was irradiated with ultraviolet rays to polymerize the first polymerizable compound and the second polymerizable compound. At this time, “USH-250BY” manufactured by USHIO INC. Was used as the ultraviolet irradiation device, and ultraviolet irradiation was performed at 100 mW for 10 minutes.
Thus, a liquid crystal display element was obtained.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87 °.
The evaluation results for this liquid crystal display element are shown in Table 1. As shown in Table 1, this liquid crystal display element showed excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 2)
Formula 1 which is the first polymerizable compound represented by the general formula (X1b) with respect to the liquid crystal-containing raw material composition LC-1 (98.5% by mass) prepared in Example 1

A compound represented by the formula (1.0% by mass) and a second polymerizable compound represented by the general formula (X2a)

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. A liquid crystal display device was obtained in the same manner as in Example 1 except that -1a was prepared and this liquid crystal-containing polymerization composition CLC-1a was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.8 °.
The evaluation results for this liquid crystal display element are shown in Table 2. As shown in Table 2, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Comparative Example 1)
A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode and further having protrusions on the surface for controlling the alignment direction of liquid crystal molecules, and driven by an active element A second substrate (pixel electrode substrate) having a transparent pixel electrode and a projection for controlling the alignment direction of liquid crystal molecules on the surface was prepared.
Next, a material for forming a vertical alignment film is applied to each of the first substrate and the second substrate by a spin coating method, and the obtained coating film is heated at 200 ° C. to thereby form a thickness on the surface of each substrate. A 100 nm vertical alignment film was formed.
Hereinafter, using these substrates on which the vertical alignment film was formed, the liquid crystal-containing raw material composition LC-1 was sandwiched in place of the liquid crystal-containing polymerization composition CLC-1 (first polymerizable compound, second polymerization compound) A liquid crystal display device was obtained in the same manner as in Example 1 except that the functional compound and the photopolymerization initiator were not used.
The evaluation results for this liquid crystal display element are shown in Table 3. As shown in Table 3, this liquid crystal display element was inferior to the liquid crystal display elements of Examples 1 and 2 in the response speed and the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 3)
A liquid crystal-containing raw material composition LC-2 containing the following compounds corresponding to the general formulas (I), (II) and (V) in the ratios shown below was prepared.

Next, the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-2 (98.0% by mass), the formula

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -2 was prepared.

Hereinafter, this liquid crystal-containing polymerization composition CLC-2 is used in place of the liquid crystal-containing polymerization composition CLC-1, and the liquid crystal-containing polymer is used by using a 3.5 μm thick spacer instead of the 3.2 μm thick spacer. A liquid crystal display device was obtained in the same manner as in Example 1 except that the thickness of the layer made of the polymerization composition was 3.5 μm.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.5 °.
Table 4 shows the evaluation results of this liquid crystal display element. As shown in Table 4, this liquid crystal display element showed excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

Example 4
Formula 1 which is the first polymerizable compound represented by the general formula (X1c) with respect to the liquid crystal-containing raw material composition LC-2 (98.3 mass%) prepared in Example 3

A compound represented by the formula (1.2% by mass) and a second polymerizable compound represented by the general formula (X2a):

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -2a was prepared, and a liquid crystal display device was obtained in the same manner as in Example 3 except that this liquid crystal-containing polymerization composition CLC-2a was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.9 °.
Table 5 shows the evaluation results of this liquid crystal display element. As shown in Table 5, this liquid crystal display element showed excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Comparative Example 2)
By the same method as Comparative Example 1, a first substrate and a second substrate on which a vertical alignment film was formed were produced.
Hereinafter, using these substrates on which the vertical alignment film was formed, the liquid crystal-containing raw material composition LC-2 prepared in Example 3 was sandwiched instead of the liquid crystal-containing polymerization composition CLC-1 (first polymerizable property). The compound, the second polymerizable compound and the photopolymerization initiator were not used), and the thickness of the layer made of the liquid crystal-containing raw material composition was replaced with a spacer having a thickness of 3.8 μm instead of the spacer having a thickness of 3.2 μm. A liquid crystal display element was obtained in the same manner as in Example 1 except that the thickness was 3.8 μm.
Table 6 shows the evaluation results of this liquid crystal display element. As shown in Table 6, this liquid crystal display element was inferior to the liquid crystal display elements of Examples 3 and 4 in the response speed and the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 5)
A liquid crystal-containing raw material composition LC-3 containing the following compounds corresponding to the general formulas (I), (II), (IV) and (V) in the ratios shown below was prepared.

Next, the first polymerizable compound represented by the general formula (X1a) ((X1a-1-1)) with respect to the liquid crystal-containing raw material composition LC-3 (98.0% by mass),

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -3 was prepared.

Hereinafter, this liquid crystal-containing polymerization composition CLC-3 was used in place of the liquid crystal-containing polymerization composition CLC-1, and the liquid crystal-containing polymer was used by using a 3.5 μm thick spacer instead of the 3.2 μm thick spacer. A liquid crystal display device was obtained in the same manner as in Example 1 except that the thickness of the layer made of the polymerization composition was 3.5 μm.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.7 °.
Table 7 shows the evaluation results of this liquid crystal display element. As shown in Table 7, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 6)
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-3 (98.1% by mass) prepared in Example 5

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.3% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -3a was prepared, and a liquid crystal display device was obtained in the same manner as in Example 5 except that this liquid crystal-containing polymerization composition CLC-3a was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.4 °.
Table 8 shows the evaluation results of this liquid crystal display element. As shown in Table 8, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Comparative Example 3)
By the same method as Comparative Example 1, a first substrate and a second substrate on which a vertical alignment film was formed were produced.
Hereinafter, using these substrates on which the vertical alignment film was formed, the liquid crystal-containing raw material composition LC-3 prepared in Example 5 was sandwiched in place of the liquid crystal-containing polymerization composition CLC-1 (first polymerizable property). The compound, the second polymerizable compound and the photopolymerization initiator were not used), and the thickness of the layer made of the liquid crystal-containing raw material composition was replaced with a spacer having a thickness of 3.5 μm instead of the spacer having a thickness of 3.2 μm. A liquid crystal display element was obtained in the same manner as in Example 1 except that the thickness was 3.5 μm.
Table 9 shows the evaluation results of this liquid crystal display element. As shown in Table 9, this liquid crystal display element was inferior to the liquid crystal display elements of Examples 5 and 6 in the response speed and the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 7)
A liquid crystal-containing raw material composition LC-4 containing the following compounds corresponding to the general formulas (I), (II) and (III) in the ratios shown below was prepared.

Next, the formula, which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-4 (98.0% by mass)

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -4 was prepared.

Hereinafter, this liquid crystal-containing polymerization composition CLC-4 was used in place of the liquid crystal-containing polymerization composition CLC-1, and a liquid crystal-containing composition was used by replacing the spacer having a thickness of 3.2 μm with a spacer having a thickness of 3.5 μm. A liquid crystal display device was obtained in the same manner as in Example 1 except that the thickness of the layer made of the polymerization composition was 3.5 μm.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 88.0 °.
Table 10 shows the evaluation results of this liquid crystal display element. As shown in Table 10, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 8)
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-4 (98.0% by mass) prepared in Example 7

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -4a was prepared, and a liquid crystal display device was obtained in the same manner as in Example 7 except that this liquid crystal-containing polymerization composition CLC-4a was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.3 °.
Table 11 shows the evaluation results of this liquid crystal display element. As shown in Table 11, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Comparative Example 4)
By the same method as Comparative Example 1, a first substrate and a second substrate on which a vertical alignment film was formed were produced.
Hereinafter, using these substrates on which a vertical alignment film was formed, the liquid crystal-containing raw material composition LC-4 prepared in Example 7 was sandwiched in place of the liquid crystal-containing polymerization composition CLC-1 (first polymerizable property). The compound, the second polymerizable compound and the photopolymerization initiator were not used), and the thickness of the layer made of the liquid crystal-containing raw material composition was replaced with a spacer having a thickness of 3.5 μm instead of the spacer having a thickness of 3.2 μm. A liquid crystal display element was obtained in the same manner as in Example 1 except that the thickness was 3.5 μm.
Table 12 shows the evaluation results of this liquid crystal display element. As shown in Table 12, this liquid crystal display element was inferior to the liquid crystal display elements of Examples 7 and 8 in the response speed and the effect of suppressing the occurrence of image sticking and dropping marks.

Example 9
Formula 1 which is the first polymerizable compound represented by the general formula (X1b) with respect to the liquid crystal-containing raw material composition LC-1 (98.5% by mass) prepared in Example 1

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -1b was prepared, and a liquid crystal display device was obtained in the same manner as in Example 1, except that this liquid crystal-containing polymerization composition CLC-1b was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.6 °.
Table 13 shows the evaluation results of this liquid crystal display element. As shown in Table 13, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 10)
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-1 (98.5% by mass) prepared in Example 1

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -1c was prepared, and a liquid crystal display device was obtained in the same manner as in Example 1, except that this liquid crystal-containing polymerization composition CLC-1c was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.9 °.
Table 14 shows the evaluation results of this liquid crystal display element. As shown in Table 14, this liquid crystal display element showed excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 11)
Formula 1 which is the first polymerizable compound represented by the general formula (X1c) with respect to the liquid crystal-containing raw material composition LC-2 (98.3 mass%) prepared in Example 3

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -2b was prepared, and a liquid crystal display device was obtained in the same manner as in Example 3, except that this liquid crystal-containing polymerization composition CLC-2b was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.8 °.
Table 15 shows the evaluation results of this liquid crystal display element. As shown in Table 15, this liquid crystal display element showed excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

Example 12
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-3 (98.1% by mass) prepared in Example 5

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.3% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -3b was prepared, and a liquid crystal display device was obtained in the same manner as in Example 5 except that this liquid crystal-containing polymerization composition CLC-3b was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.5 °.
Table 16 shows the evaluation results of this liquid crystal display element. As shown in Table 16, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 13)
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-3 (98.1% by mass) prepared in Example 5

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.3% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -3c was prepared, and a liquid crystal display device was obtained in the same manner as in Example 5, except that this liquid crystal-containing polymerization composition CLC-3c was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.3 °.
Table 17 shows the evaluation results of this liquid crystal display element. As shown in Table 17, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 14)
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-4 (98.0% by mass) prepared in Example 7

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -4b was prepared, and a liquid crystal display device was obtained in the same manner as in Example 7 except that this liquid crystal-containing polymerization composition CLC-4b was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.4 °.
Table 18 shows the evaluation results of this liquid crystal display element. As shown in Table 18, this liquid crystal display element showed excellent contrast and response speed, was excellent in various properties as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

(Example 15)
Formula 1 which is the first polymerizable compound represented by the general formula (X1a) with respect to the liquid crystal-containing raw material composition LC-4 (98.0% by mass) prepared in Example 7

A liquid crystal-containing polymerization composition CLC is obtained by adding a compound represented by the formula (0.4% by mass) and further adding a photopolymerization initiator “Igacure 651” (0.1% by mass) and dissolving it uniformly. -4c was prepared, and a liquid crystal display device was obtained in the same manner as in Example 7 except that this liquid crystal-containing polymerization composition CLC-4c was used.
In this liquid crystal display element, the pretilt angle θ given to the liquid crystal molecules was maintained even when voltage application was stopped, and the value was 87.1 °.
Table 19 shows the evaluation results of this liquid crystal display element. As shown in Table 19, this liquid crystal display element exhibited excellent contrast and response speed, was excellent in various characteristics as a liquid crystal display element, and was also excellent in the effect of suppressing the occurrence of image sticking and dropping marks.

DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11 ... 1st board | substrate, 12 ... 2nd board | substrate, 13 ... Liquid crystal layer, 14 ... Common electrode, 15 ... Pixel electrode, 18 ...・ Color filters, 19 ... Liquid crystal molecules

Claims

A liquid crystal layer containing a liquid crystal composition is sandwiched between a first substrate having a common electrode and a color filter layer and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels. A liquid crystal display element,
Between the first substrate and the second substrate and the liquid crystal layer, without an alignment film, having an alignment control layer formed from two or more polymerizable compounds,
The pixel has two or more regions having different pretilt directions,
The liquid crystal composition has the following general formula (I)

(Wherein R 1α and R 2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms) 8 represents an alkenyloxy group, Q 1 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l 1 represents 1 or 2, and when l 1 is 2, Q 1 may be the same or different.), And the following general formula (II)

(Wherein R 3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R 4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and Q 2 represents 1 , 4-phenylene group or trans-1,4-cyclohexylene group, l 2 represents 0, 1 or 2, but when l 2 is 2, two Q 2 are the same or different at best, G 1 is a single bond, -CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - contains a representative) and a compound represented by - CF 2 O-or -OCF 2. The liquid crystal display element characterized by the above-mentioned.
The liquid crystal display element according to claim 1, wherein the pixel electrode has a slit.
2. The liquid crystal display element according to claim 1, wherein at least one of the first substrate and the second substrate has a structure that defines a pretilt direction.
The two or more polymerizable compounds are at least one selected from the group consisting of a first polymerizable compound selected from the group consisting of monofunctional (meth) acrylates and a bifunctional (meth) acrylate. The liquid crystal display element according to any one of claims 1 to 3, further comprising a second polymerizable compound.
The first polymerizable compound is represented by the following general formula (X1a)

(In the formula, A 1 represents a hydrogen atom or a methyl group,
A 2 represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. May be)
A 3 and A 6 are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 18 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 17 carbon atoms).
A 4 and A 7 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are such that oxygen atoms are not directly bonded to each other) And each independently may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group are each independently a halogen atom. Which may be substituted with an atom or an alkyl group having 1 to 9 carbon atoms).
k represents 1 to 40,
B 1 , B 2 and B 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups in the alkyl group are In addition, as the oxygen atoms are not directly bonded to each other, each may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more of the alkyl groups may be substituted. Each hydrogen atom may be independently substituted with a halogen atom or a trialkoxysilyl group having 3 to 6 carbon atoms), or the following general formula (Ib)

(In the formula, A 9 represents a hydrogen atom or a methyl group,
A 8 represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other, -CO-, -COO- or -OCO- may be substituted, and one or more hydrogen atoms in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group. A group represented by formula (1). However, among the total of 2 k + 1 B 1 , B 2 and B 3 , the number of the group represented by the general formula (Ib) is 0 or 1. ) A compound represented by
The following general formula (X1b)

(Wherein R 7 represents a hydrogen atom or a methyl group,
6-membered rings T 1 , T 2 and T 3 are each independently

(Where m represents an integer of 1 to 4),
n 4 represents 0 or 1,
Y 1 and Y 2 are each independently a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —C≡C—, —CH═CH—. , —CF═CF—, — (CH 2 ) 4 —, —CH 2 CH 2 CH 2 O—, —OCH 2 CH 2 CH 2 —, —CH 2 ═CHCH 2 CH 2 — or —CH 2 CH 2 CH = CH-
Y 3 represents a single bond, —COO— or —OCO—,
R 8 represents a hydrocarbon group having 1 to 18 carbon atoms. ) A compound represented by
And the following general formula (X1c)

(Wherein R 70 represents a hydrogen atom or a methyl group,
R 71 represents a hydrocarbon group having a condensed ring. And at least one selected from the group consisting of compounds represented by:
The second polymerizable compound is represented by the following general formula (X2a)

(Wherein R 3 and R 4 each independently represents a hydrogen atom or a methyl group,
C 4 and C 5 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyridazine-3,6- Diyl group, 1,3-dioxane-2,5-diyl group, cyclohexene-1,4-diyl group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6 -Diyl group, phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, 2,6-naphthylene group or indane-2,5-diyl group (among these groups, 1,4-phenylene group) 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group and indane-2,5-diyl group each independently have one or more hydrogen atoms. Fluorine atom, Represents atom, a methyl group, may be substituted with a trifluoromethyl group or a trifluoromethoxy group. The)
Z 3 and Z 5 are each independently a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups in the alkylene group are such that oxygen atoms are not directly bonded to each other; Each independently substituted with an oxygen atom, —CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkylene group are each independently a fluorine atom, methyl Group or an ethyl group, which may be substituted)
Z 4 is a single bond, —CH 2 CH 2 —, —CH 2 O—, —OCH 2 —, —CH 2 CH 2 O—, —OCH 2 CH 2 —, —CH 2 CH 2 CH 2 O—, —OCH 2 CH 2 CH 2 —, —CH 2 CH 2 OCO—, —COOCH 2 CH 2 —, —CH 2 CH 2 COO—, —OCOCH 2 CH 2 —, —CH═CH—, —C≡C— , —CF 2 O—, —OCF 2 —, —CH═CHCOO—, —OCOCH═CH—, —COO— or —OCO—,
n 2 represents 0, 1 or 2, and when n 2 is 2, a plurality of C 4 and Z 4 may be the same or different. The liquid crystal display element according to claim 4, which is at least one selected from the group consisting of compounds represented by:
The liquid crystal according to any one of claims 1 to 5, further comprising a passivation film on at least one of the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer. Display element.
The flattening film is provided on at least one of the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer according to any one of claims 1 to 5. Liquid crystal display element.
A liquid crystal layer containing a liquid crystal composition is sandwiched between a first substrate having a common electrode and a color filter layer and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels. A method of manufacturing a liquid crystal display element having two or more regions having different pretilt directions in the pixel,
An alignment film is not provided between the first substrate and the second substrate, and the following general formula (I)

(Wherein R 1α and R 2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms) 8 represents an alkenyloxy group, Q 1 represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l 1 represents 1 or 2, and when l 1 is 2, Q 1 may be the same or different.), A compound represented by the following general formula (II)

(Wherein R 3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R 4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and Q 2 represents 1 , 4-phenylene group or trans-1,4-cyclohexylene group, l 2 represents 0, 1 or 2, but when l 2 is 2, two Q 2 are the same or different at best, G 1 is a single bond, -CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CF 2 O- or -OCF 2 -. compounds represented by the representative) a, and 2 Sandwiching a liquid crystal-containing polymerization composition containing at least one polymerizable compound;
By irradiating an active energy ray between the pixel electrode and the common electrode while applying a voltage for applying a pretilt angle to the liquid crystal molecules in the liquid crystal-containing polymerization composition, the two or more types are used. And forming an alignment control layer between the first substrate and the second substrate and the liquid crystal layer using the liquid crystal-containing polymerization composition as the liquid crystal composition. A method for producing a liquid crystal display element.
The method for producing a liquid crystal display element according to claim 8, wherein the active energy rays are ultraviolet rays having a plurality of spectra.
10. The method of manufacturing a liquid crystal display element according to claim 8, wherein the pixel electrode has a slit, or at least one of the first substrate and the second substrate has a structure that defines a pretilt direction.